Water-in-oil lubricant and hydraulic fluid



basic'polyvalent metal organic sulfonate,-.the metals of stituentichlorine atoms.

o U111td States PatentO ce r ,t t r v p a a Patented Oct. 1959 both compounds being of group II metals of the periodic 2 907 714 table and having an atomic number of from 12 to 56, and I p j i I (3) an oi1-soluble chlorohydrocarbon thiocarbonate ester "W ATER-IN-OIL LUBRICANT AND HYDRAULIC The oil-soluble basic polyvalenfmetal aromatic car- 3 F U D f I 5 boxylates ofthe group II metals of the periodic table 3' having an atomic number of from 12 to 56 inclusive and Charles Francrs and John J. Weaver, Mart nez, Cahfl, r a a ssr 5353222: szs zzissfisss assss r 1 e are r 2 r a a l I p s i 7 j and zincsalts of hydrocarbon substituted benzorc, salir N0 D T E-Q PP Q 9 1 o cylic, resorcylic, anthranilic and naphthoicacids such as x Serial 3 95 1 the basic calcium, barium, magnesium and/or zinc salts L 33 1 of C C -alkylbenzo1c,Q -C -alkylsal1cy11c, C C almm (C j kylnaphthorc acrds and rmxtures thereof.

I 'j p n The preferred salts are the basic barium, calcium, magi This invention relates to'improved musion lubricants 15 163mm, "f Zinc} salts s a y a f "1 and hydrauli c fiuids. More particularly, it pertains to gi g fg iii l or of t f Yl f g 32145 water-ln-oil emulsronlubrlcants especially, useful for slow 1 w 1.: z groutps con 5 3 speed diesel engines andiasfire-resistant hydraulic fluids y a1 a 1 t u asllc F 1 d @112 whlijcih possess good lubrrdcatmg propertles and which are g fiy g gi ggy ig g ggg g 2235;2 :5 y g t r u v a a i gf gigFffigg i fif fififi i emulsions processes described in US. Patents 2,409,687 or 2,616,910. ar e iisefultas' coblants and lubricants in metal working 015 sulfonate? are oil'soluble basic Polyvalent metal erations and as rust and corrosion inhibitors, their use Orgamc f r of which sulfpnates of the as eh in .lubricagts andrasihydmuligfluidsyhas196m metalls of fgrgup II1 gftthe5 gerrocirc table havingf an ezzrltomrcci ited." Under engine operating conditions, emulsions g ennum F il f gg alk I! fh tl g f f gl erally lack deslred lubricity and cause wear and corrosion. i zgg i g 5 23 51; 52% g g n es fin l aria .Fluid compositions for use in hydraulic systems y I shouldbefire-resistant and non-corrosive. 1 They should g ;$,ig l q p g s m 1-l f be capable of preventing wear and be thermally stable and m if; 350! g g i n m PP i n resistant to oxidation. jVarlouscomposltrons have been a 92 t 2E q Pro-pp ed as -i f- 2 g olub l e basic czfilciurri has; ir ragn siiin'i zfn d zinc Zea-a 5:23:11? 'c l izr ii isms -a i1 d gl j f d g ggggi tertiarybutylnaphthalenefsulfonates, dinony-l naphthalene esters offcarboxylic acids cause swelling of r ubber, the? i g t eosnzfig niligwllliientfizneofsulfonates, waxphenol sulfu- Organ: h9 P r l g fi f 2 125 1 lth By a basic salt as used with reference to the aromatic ogen-contarrrmgma err s en 0 y oyze o pro uce t corrosive materials, emulsion lack wearresistant; properi gi i r 9 2 ha the;amum

senta t azar. a 1

It i s an object fof this invention to provide a emulsion 4Q ztg gf g iu g 1161132111? szf l a y u ricating properties. 0, er 0 ject is to provr e 'a j r p fluid which is a satisfactory lubricant for low speed diesel 283 i g i: to 1000% and 9 .7 r .0 oh gg zzi f i ggg g a g ggjg gg ig g i gg gi The ell-soluble chlorohydrocarbyl hydrocarbylthiocarx; and does not cause wear. Still another object of this gg prefarfibly a volychloroalklyl hydrocarbyk invention is to provide an emulsion lubricant and firepear e m lm' resistant hydraulic fluid of good lubricating quality even RCYTR'CI;

when subjected to various adverse conditions of tempera t P r it as a W s 60 n meso eratrn on s r es or mrcertar a g g g g it n twice the number of carbon atoms in R, preferably it is These an Lethe: Objects are anmplishedi1;! no linoredthairlth same fas the number of carbon atoms 7 with this 'inventionby providing a water-in-oil" emulsion Ll s? s i i gg f f g gg g b f 5: a of which is 9 Q to about 45% its d least 4 and R and R are hydroi ar b ri ia ciicals c h tii fromflliout 5 9 aPout 011 Phase the sn inga totaltogether of ,at least 12 carbon atoms, at least 9 of mmor Pmmmts of tilree one of them and preferably R being an aliphatic hydrol addlilYeS, n m y (1') wb P -P carbon radicalof at least 10 carbon atoms, preferably valent metal aroma CaIYbQXYIatB, nv -s l 1 from 12 to 30 carbon atoms and having at least four sub- These chlorohydrocarbyl thiocarbona-te esters are suitablyprepared by the reactionfof polychlorohydrocarbons with less than the stoichiometrically equivalent amount of an alkali metal or of analkaline earth metal hydrocarbyl thiocarbonate, with the formation of the alkali 'xanthate, potassium butyl' xanthate, sodium amyl xanthate; and potassium. amyl xanthate and alkal'ii metal lower aralkyl xanthates, such as potassium benzyl xanthate. The monoand tri-thiocarbonate ester salt reactants are illustrated by the substances more simply designated by their formulae: a 1

CHgO' CO- SNa, CH S ONa, CH CS- ONa, I "CH S'CSSNa, C H S CS SK, CgHqS -CS'- SK and corresponding otherester-salts. containing hydrocarbon radicals of from. 1 to 7 carbon atoms.

The thiocarbonate ester-salts are suitably reacted with.

various polychlorinated hydrocarbons in such proportions as to. leave. at least four chlorine atoms. in the resulting.

thiocarbonate full ester.. The polychlorinated. hydrocarbons are preferably polychlorinated aliphatic hydrocarbons of from about 2 to about 30 carbon atoms per molecule. Mixtures of polychloroalkanes, including. cyclic and. acylic alkanes, are particularly useful vSome readily available materials which may be used are chlorinated naphtha, chlorinated paraffinic lubricating oils, chlorinated paraffin 'wax and' chlorinated rubber.-

As indicated, the reactants are reacted in proportions V such that the final. product contains both chlorine and thiocarbonate groups. The-amounts of chlorine and. sulfur in, the final product can vary over a. wide range such as from. about 25 to about 40% by weight chlorine andfrom about 7 to about 15% by weight sulfur.v

An illustrative product of this type can. beprepared as described in the following, example:

EXAMPLE I Petroleum naphtha; (Stoddardsolvent) was chlorinated by bubbling chlorine gas through it. until it contained about 52%- byweight of chlorine. 225: parts by weight of the: chloronaphtha. was mixed with about 400 parts of acetone and-z 100 parts of. potassium amyl trithiocarbonate'. Themixture was refluxed with stirring on a; water bath and-heatedforaboutone and one-half hours; after'which it was cooled and filtered to remove the. potassium: chloride. The: acetone. was removed by distillation, after which. benzene was: added and distilled ofi to insure removal of water from the product. The resulting product was a bright liquid, soluble in oil, and a typical analysis showed a chlorine content of 35% and a sulfur content of about or a trithiocarbonate (divalent CS cone tent ofabout 11.3%;

Similar-polychloronaphtha'alkyl xanthates are marketed by the Monsanto ChemicaIJCOmpany under the name SantopoidjS. A typical Santopoid S (polychloroa naphtha alkyl xanthate) has the following. characteristicsz sp. gr. 1.19 at 6'0/60' Fl; flash point 250" E; viscosity 5 p 4 about 2% to about 4% while the chlorohydrocarbyl thiocarbonate compound is used from about 3'%'to about 10% by weight, based on the amount of oil in the emulsion.

In addition to the above. three essential additivesand mixtures thereof it is preferred to use in such compositions small amounts of from about 0.01% to about 2%, preferably from about 0.2% to about 1% of phenolic, amine and/ or metal thiophosphate anti-oxidants such as alkyl phenols, e.g., diand trialkyl phenols, for instance 2,4-, 2,3-, 3,4-, 2,6- and 3,5-diamylphenol, 2,4-dimethyl- 6-tert.butylphenol, 2,6-ditert.butyl-4-methylphenol; arylamines such as phenyl-alpha-naphthylamine o'r phenylbeta-naphthylamine; metal thiophosphates such as calcium or zinc dimethyl cyclohexyldithiophosphate; dyes such as various oil-soluble dyes e.g. Naphthol yellow,' Sandoz yellow, methylene blue, alizarin compounds etc.; antifoaming agents e.g., silicone. polymers (DC-200 fluids ranging in viscosity in centistokes from 100 to 1000 at 250? C.) or silicone type A fluid made by Dow Corning Co. and described in US. Patents 2,563,588- and 2,662,055- and' mixtures thereof. I

The aqueous phase of the water-in-oil' emulsion should range from'about 20% to about 45% and preferably from about 30% to about 40% by weight of the emulsion. The oil phase containing the additives comprise the balance of the emulsion; 'The oil maybe entirely a hydrocarbon oil of wide viscosity range, e.g., from less than .50 SUS at 100 F. to 150 SUS at 210 F. .Oils of. this type can be obtained from various crudes such as parafiinic, naphthenic or mixed base crudes; refined oils in the lubricati'ngoil viscosity range are preferred. 0n the other hand, the hydrocarbon oil may be blended with ,fixed oils such ascast'or oil, l'ard' oil and the like and/or with. synthetic lubricants such as polymerized olefi'ns, organic esters. of organic and inorganic acids, e.g., di-2- ethylhexyl sebacate, dioct'yl'phthal'ate, trioctyl phosphate; polymeric tetrahydrofuran, polyalkyl silicone polymer,

A straight mineral lubricating oil, having. a viscosity.

index of at least 50 and ranging in. viscosity at 100F. of from to 400 SUS, is usually preferred. When it is derived, from a lubricating oil stock of. low viscosity index it is readily provided as raifinate in-v a selective solvent' extraction process as is well. understood in. the

art. The emulsion can be. prepared by adding. therequiredi amount of water to an, oil. containing. thethree essential additives, namely an oil. containing the two base:

salts and the thiocarbonate-containing compound, while constantly stirring. the mixture Heating. theemulsion during or after it is prepared is not necessary.. If desired,- the emulsion can be homogenized to insure a homogene ouseomposition. Instead ofmaking the f nished; emul;

sion,ft'he oil. concentrate containing the'essential; additives namely the twobasic salts and the chlorohydrocarbyl,

thiocarbonate: compound canbe prepared and the requiredamount of water added. when theemulsion: lubricantis;

In this waystorage, and shipping costs;

ready for use. can be. greatly reduced;

A finished emulsion fluid [composition (All of the in: vention was prepared by slowly adding 40%: water to a; vessel containing 2% each of oil-soluble basic calcium. petroleum sulfonate (1,80% excess base). and oil soluble basic calcium C 4 alkyl salicylate (50% excess: base) and 5% additive Example. I dispersed in 5.1%. mineral 'oil of SUS' at 100" FL The entire mixture. was passed through a colloid mill" where it was agitated' untila homogeneous water-in-oil' emulsion? was formed' A similar composition (A'); was prepared but. instead of using a colloid mill to form a homogeneous emulsion,

a homogehizer was used.

Other compositions which illustrate emulsions of this invention are: l

6 acid resulted incompositions haying poor emu'lsionastability and viscosity. I; H. In thepipe cleaner test, compositions Athrough-D Percentwt. Percent passed over 50 cycles while mineral oil or mineral oil *i of e fi 5 contaming 4% of Ca petroleum sulfonates and/or- Ca 111 Total in 011 Em C1242 alkyl salicylate ignited after about .5-cycles.

' Compositions of thisiinvention are particularly suitable Composition 1;; y for use in diesel engines, in dictating-machines; in L 2 2 permanent mold machines in steel mill equipmentsuch-as Basic calbcium o alkyl salicylate 50% 1 2 2 coke pushers, pipe coupling tighteners, combustion control excess ase v p "Sanwpoid (cmomnaphtha methyl mechamsms, plast c molding presses. and glasssblowing 2 fii i 'B'TI Z' tfil'h i"""" "0 machmes and i i i i i A 91' 181 ll -II16 eno n, Phenyl-alph arnabhthylam in 0.06 0.1 We F P L V now Dye (Sandoz Ohem Co) 0. 01s 0. 0s 1. A water-m-oil emulsion lubricant and hydrauhc fluid SUS at 100 F fi' g which is from about to about water phase and con enial 1 u t v 5 from about 55% to about 80% oil phase, the oil phase, L2 2 being essentially a mineral oil containing from about Basic bau m 0 alkyl sahcylate 1 0.5% to about 12% each, based on the 011, Of an 011- fgfigi fi u" 555 55555555555,1- 2 soluble basic alkaline earth metal organic sulfonate 2 a x thfi w g-g 0 g 20 and an oil-soluble basic alkaline earth metal alkyl salicyl- ;if i g l g i gj jj Mg ate from about 3% 1golaboutfll0% of an oil-soluble chlo- 8 0w y OZ 01 rme-containmg nap a xau ate.

5,152 2. A water-m-oil emulsion lubricant and hydraulic fluid gg g zg g djmm 1 N 11th alene SUL which is from about 20% to about 45 water phase and mate (530% x g ji 2 25 from about to about oil phase, the oil phase 31 9 calclllm W sallcylate 7 EXCESS 2 3 3 being essentially a mineral 011 contammg from about 2% 2 1 to about 4% each, based on the oil, of an oil-soluble basic 2% alkaline earth metal organic sulfonate and an oil-soluble Composition 1 i basic alkaline earth metal alkyl salicylate and from about Bfislc calmumfimonylnaphthalene sulfo- 30 3% to about 10% of an oil-soluble chlorine-containing nate (50% excess base) 2 3. 3 Basic gzalcium diwaxbenzoate (25% excess 2 3 3 naphtha Xant ate.

3S6 3. The composition of claim 2 containing in the emul- Ohlorona hthabut l anth t 2 3.3 Mineral 8'1 54 9 ,1 mm from 0.01% to 2% of an oil-soluble anti-oxidant Water selected from the group consisting of phenolic and aryl- I 35 amine compounds. Theoutstandmg properties which compositions of 111 118 4. A water-in-oil emulsion lubricant and hydraulic invention possess are shown m Table I. The stablllty fluid which is from about 30% to about 40% water phase was determined by measuring the amount of water and 011 and from about 70% to about 60% oil phase; the oil separatronat 140 F. from a ml. test sample. The phase being essentially a mineral oil containing from load carrying properties were determined on the Timken 40 b t 2% t b t 4%. a h, b d on h il, f il. machine Whlle the Wear reslstant properties of th em lsoluble basic calcium petroleum sulfonate, and oil-soluble sons were determined by measunng the amount of wear basic calcium C1842 alkyl salicylate and from about 3% 111 f vlckfirs Vane P p f clrcllto about 10% of oil-soluble polychloronaphtha xanthate. latlng the test fluid under conditions mdicated m Table I. 5, Th composition of 1 i 4 containing i h l- The fire-resistance Was determined by the pipe cleaner 45 ion from about 0.01% to about 1% each of an oiltest described in Lubrication Engineering, March-April soluble alkylphenol and an oil-soluble arylamine. 1955, pages 86 87. 6. A water-in-oil emulsion lubricant and hydraulic fluid Table I Oompnsitirm B X 1 Y 2 Emulsion Stability at F.:

Separation, Percent Vo1.- Oil Water 011 Water Oil Water 4 days l trace 1 trace 4 Trace 13 days- 3 slight 8 slight 25 18 days- 6 slight 6 slight complete separation Timkeu Test at F./l0 mm Failure Load, lb 20 5 Pump Wear Test:

Total wear of Vancs and Ring 0.165 0.200 failed 0.300 (at 100 Combined (300 hr. at 1,000 psi. hr.). fluid temp. 150 F.), grams. Equilibrium Wear Rate of Vanes and Ring Combined, grams.l,000 hr.:

1,000p.s.i 0. 49 0.38 tailed.

0.66 0.27 0. 75 8.4 0.75 failed.

1 Composition X [57% mineral oil (100 SUS at 100 F.)+1.2% basic calcium petroleum sulfonate+1.2% basic calcium 0 alkyl salicylate+0.3% 2,6-ditcrtbuty1-4-methyl phenol +0.06% phenyl-alpha-naphthylamine+0.018% Yellow Dye+40% water].

2 Composition Y [54% mineral 0il+l.2%

basic calcium petroleum sulfonate+1.2% basic The substitution of other wear inhibitors for the chloroxanthate in composition B of this invention, such as chlorinated paraflin Wax, zinc cyclohexyl dithiophosphate which is from about 40% water phase and about 60% oil phase, the oil-phase being essentially a mineral oil containing from about 1% to about 2% each of oilor the zinc and cadmium salts of diamyl dithiocarbamic 75 soluble basic calcium petroleum sulfonate and oil-soluble to about 10% of polychloronaphtha xan thate;

7 basic calcium C alky1salicylate andfrom about 3% 75 The composition of claim 6 containing inthe emulsion fmni ab'out 0201' to about 1% each of 2,6-di-tert butyl-4 m'ethyl phenol andi phenylalpha-naphthylamine.- 8. A mineral :oil concentrate composition adapted for making stabIe water-in-oil emulsion. lubricant and bydiau'licfluid: consisting essentially of a mineral oil con mining-from about 015% to about 12% each of' an oils'olubl'e basic alkaline earth metal petroleum. sulfonate, oilI-soluble'basic alkaline eartm m'etal C1842 al-kyl salicylate' and oil-soluble polychloronaphthaXanthate; 9. A mineral oil concentratecomposition adapted' for makingstable: water=in-oi1' emulsiom lubricant and hy draulic fluidi consisting essentiallyof a mineral oil contain- 7 ing from about 0.5% to about 12% eachof an oil'-;

soluble basic calcium petroleum sulfonate, oil-soluble basic calcium C alkyl salicylate and oil-soluble polychloronaphtha xanthate.

References Cited in the file of this patent UNITED STATES PATENTS 2,153,495 Berger et a1 Apr. 4, 1939 2,153,496 Berger et a1. Apr. 4, 1939 2,466,647 Stern Apr. 5, 1949 2,744,870 Stillebroer May 8, 1956 2,820,007 7 Van Der Minne et :11. -Jan. 14, 1958 

1. A WATER-IN-OIL EMULSION LUBRICANT AND HYDRAULIC FLUID WHICH IS FROM ABOUT 20% TO ABOUT 45% WATER PHASE AND FROM ABOUT 55% TO ABOUT 80% OIL PHASE, THE OIL PHASE BEING ESSENTIALLY A MINERAL OIL CONTAINING FROM ABOUT 0.5% TO ABOUT 12% EACH, BASED ON THE OIL, OF AN OILSOLUBLE BASIC ALKALINE EARTH METAL ORGAN SULFONATE AND AN OIL-SOLUBLE BASIC ALKALINE EARTH METAL ALKYL SALICYLATE FROM ABOUT 3% TO ABOUT 10% OF AN OIL-SOLUBLE CHLORINE-CONTAINING NAPHTHA XANTHATE. 